Organometallic compound having high metathesis activity and method for preparation thereof, methathesis reaction catalyst comprising the compound, method of polymerization using the catalyst, and polymer produced by the method of polymerization

ABSTRACT

The present invention provides an organometallic compound represented by the general formula (1) or (2), process for producing the same, metathesis reaction catalyst containing the same, polymerization process using the same catalyst and polymer produced by the same polymerization process:

TECHNICAL FIELD

The present invention relates to a novel organometallic compound of highmetathesis activity, process for producing the same, metathesis reactioncatalyst containing the same, polymerization process using the samecatalyst and polymer produced by the same polymerization process, moreparticularly a novel organometallic compound excellent in stability tooxygen, metathesis reactivity and reaction controllability, process forproducing the same, metathesis reaction catalyst containing the same,polymerization process using the same catalyst and polymer produced bythe same polymerization process.

BACKGROUND ART

The metathesis reaction has been widely used in various industrialareas, e.g., for synthesis of monomers for the medical area, andproduction of molded articles excellent in mechanical strength, heatresistance, dimensional stability or the like by ring-openingpolymerization in a mold, e.g., by reaction injection molding(hereinafter sometimes referred to as RIM), of a norbornene-basedmonomer, e.g., dicyclopentadiene (hereinafter sometimes referred to asDCPD), which is a typical representative monomer for metathesispolymerization.

The conventional metathesis process uses a catalyst which exhibits themetathesis activity by reacting the catalyst precursor for the activecatalyst, e.g., molybdenum or tungsten, with an alkyl metal in a system,as disclosed by, e.g., Japanese Patent No.3,038,825. However, such aprocess is greatly limited by, e.g., reaction environments, because thealkyl metal is a water-reactive reagent.

Japanese Patent Laid-Open No.11-510807 discloses a ruthenium-basedmetathesis catalyst as the one which can solve the above problems. Ithas been attracting attention as a catalyst exhibiting excellentmetathesis activity without being deactivated even in the presence ofmoisture or oxygen. However, it is not activated as an alkyl metal orthe like in a system but exhibits activity as a single complex compound.As a result, the reaction starts as soon as it is brought into contactwith a metathesis-reactive monomer, to cause problems, one of which isdispersion of the catalyst or the like becoming the rate-determiningstep. This may be a detrimental problem when a crosslinkable monomer,e.g., dicyclopentadiene, is to be polymerized, because this can greatlylimit the process operation or fluctuate properties of the productpolymer. One of the commonly known countermeasures is incorporation oftriphenyl phosphine or the like in the system to retard thepolymerization process. This, however, may cause problems related toproduct safety, resulting from contamination of the product withphosphorus or the like.

It is an object of the present invention to provide a novelorganometallic compound excellent in stability to oxygen, metathesisreactivity and reaction controllability, in order to solve the aboveproblems. It is another object of the present invention to provide aprocess for producing the same. It is still another object of thepresent invention to provide a metathesis reaction catalyst containingthe same. It is still another object of the present invention to providea polymerization process using the same catalyst. It is still anotherobject of the present invention to provide a polymer produced by thesame polymerization process.

DISCLOSURE OF THE INVENTION

The inventors have prepared, after having extensively studied to solvethe problems involved in the conventional metathesis reaction catalyst,a novel organometallic compound containing ruthenium or osmium andsilicon to find that it is excellent in stability to oxygen, reactioncontrollability and metathesis reactivity. The present invention isdeveloped based on this knowledge.

The first aspect of the present invention provides an organometalliccompound containing ruthenium or osmium and silicon, represented by thegeneral formula (1):

wherein, M is ruthenium or osmium; R₁ is hydrogen atom, an alkenyl groupof 2 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, aryl groupof 6 to 20 carbon atoms, carboxyl group of 2 to 20 carbon atoms, alkoxygroup of 2 to 20 carbon atoms, alkenyloxy group of 2 to 20 carbon atoms,aryloxy group of 6 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20carbon atoms, alkyithia group of 2 to 20 carbon atoms, alkylsilyl groupof 2 to 20 carbon atoms, arylsilyl group of 2 to 20 carbon atoms orferrocene derivative, as required, with a phenyl group substituted withan alkyl group of 1 to 5 carbon atoms, halogen atom or alkoxy group of 1to 5 carbon atoms; R₂ to R₄ are each hydrogen atom, an alkenyl group of2 to 20 carbon atoms, alkyl group of 2 to 20 carbon atoms, aryl group of6 to 20 carbon atoms, carboxyl group of 2 to 20 carbon atoms, alkoxygroup of 2 to 20 carbon atoms, alkenyloxy group of 2 to 20 carbon atoms,aryloxy group of 6 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20carbon atoms, alkylthio group of 2 to 20 carbon atoms, alkylsilyl groupof 2 to 20 carbon atoms, arylsilyl group of 2 to 20 carb atoms orferrocene derivative, which may be the same or different andsubstituted, as required with a phenyl group substituted with an alkylgroup of 1 to 5 carbon atoms, halogen atom or alkoxy group of 1 to 5carbon atoms; when R₁ is hydrogen atom, at least one of R₂ to R₄ isphenyl, isopropyl or t-butyl group; X₁ and X₂ are each an anionicligand, which maybe the same or different; and L₁ and L₂ are each aneutral electron donor, which may be the same or different and at leastone of L₁ and L₂ is a phosphorus-based ligand; where 2 or 3 of X₁, X₂,L₁ and L₂ may together form a multidentate, chelated ligand.

The second aspect provides the organometallic compound of the firstaspect, wherein R₁ in the general formula (1) is a substituent selectedfrom the group consisting of phenyl, anisyl, t-butyl, n-butyl, n-propyl,isopropyl, ethyl, methyl, methoxyrnethyl, ferrocenyl and trimethylsilylgroup; the third aspect provides the organometallic compound of thefirst aspect, wherein each of R₂ to R₄ in the general formula (1) is asubstituent selected from the group consisting of methyl, ethyl,isopropyl, t-butyl, cyclohexyl and phenyl group; and the fourth aspectprovides the organometallic compound of the first aspect, wherein eachof L₁ and L₂ in the general formula (1) is a phosphorus-based ligand.

The fifth aspect of the present invention provides an organometalliccompound containing ruthenium or osmium and silicon, represented by thegeneral formula (2):

wherein, M is ruthenium or osmium; R₅ is hydrogen atom, an alkenyl groupof 2 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms,substituted phenyl group of 7 to 20 carbon atoms, carboxyl group of 2 to20 carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy groupof 2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms,alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20carbon atoms, alkylsilyl group of 2 to 20 carbon atoms or arylsilylgroup of 2 to 20 carbon atoms; R₆ to R₈ are each hydrogen atom, analkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbonatoms, aryl group of 6 to 20 carbon atoms, carboxyl group of 2 to 20carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms,alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20carbon atoms, alkylsilyl group of 2 to 20 carbon atoms, arylsilyl groupof 2 to 20 carbon atoms or ferrocene derivative, which may be the sameor different and substituted, as required, with a phenyl groupsubstituted with an alkyl group of 1 to 5 carbon atoms, halogen atom oralkoxy group of 1 to 5 carbon atoms; when R₅ is hydrogen atom, at leastone of R₆ to R₈ is phenyl, isopropyl or t-butyl group; X₃ and X₄ areeach a halogen atom, which may be the same or different; and L₃ and L₄are each a neutral electron donor, which may be the same or different;where 2 or 3 of X₃, X₄, L₃ and L₄ may together form a multidentate,chelated ligand.

The sixth aspect provides the organometallic compound of the fifthaspect, wherein R₅ in the general formula (2) is a substituent selectedfrom the group consisting of tolyl, anisyl, t-butyl, n-butyl, n-propyl,isopropyl, ethyl, methyl, methoxymethyl and trimethylsilyl group; theseventh aspect provides the organometallic compound of the fifth aspect,wherein each of R₆ to R₈ in the general formula (2) is a substituentselected from the group consisting of methyl, ethyl, isopropyl, t-butyl,cyclohexyl and phenyl group; and the eighth aspect provides theorganometallic compound of the fifth aspect, wherein each of L₃ and L₄in the general formula (2) is a phosphorus-based ligand.

The ninth aspect of the present invention provides a process forproducing the organometallic compound of one of the first to eighthaspects, wherein a precursor for a ruthenium or osmium complex andneutral electron-donating ligand compound are mixed with each other forthe ligand-exchanging reaction.

The tenth aspect of the present invention provides a metathesis reactioncatalyst containing the organometallic compound of one of the first toeighth aspects.

The 11^(th) aspect of the present invention provides a metathesispolymerization process for producing a metathesis-reactive monomer inthe presence of the metathesis reaction catalyst of the tenth aspect.

The 12^(th) aspect of the present invention provides the metathesispolymerization process of the 11^(th) aspect, wherein themetathesis-reactive monomer is a norbornene-based monomer of bicyclic orhigher structure; the 13^(th) aspect of the present invention providesthe metathesis polymerization process of the 11^(th) aspect, wherein thenorbornene-based monomer is a compound selected from the groupconsisting of norbornene, substituted norbornene, dicyclopentadiene andtricyclopentadiene; the 14^(th) aspect of the present invention providesthe metathesis polymerization process of one of the 11^(th) to 13^(th)aspects, wherein 2 or more metathesis-reactive monomers arecopolymerized.

The 15^(th) aspect of the present invention provides the metathesispolymerization process of one of the 11^(th) to 14^(th) aspects, whereina reaction-adjusting agent is further incorporated.

The 16^(th) aspect of the present invention provides the metathesispolymerization process of the 15^(th) aspect, wherein thereaction-adjusting agent is an acidic component; and the 17^(th) aspectof the present invention provides the metathesis polymerization processof 16^(th) aspect, wherein the acidic component is a Bronsted acid(protonic acid).

The 18^(th) aspect of the present invention provides the metathesispolymerization process of one of the 11^(th) to 17^(th) aspects, whereina reaction-controlling agent is further incorporated.

The 19^(th) aspect of the present invention provides the metathesispolymerization process of the 18^(th) aspect, wherein thereaction-controlling agent is a compound having a metathesis-reactiveunsaturated bond; the 20^(th) aspect of the present invention providesthe metathesis polymerization process of 19^(th) aspect, wherein thecompound having a metathesis-reactive unsaturated bond is selected fromthe group consisting of a vinyl ester, vinyl sulfide, vinyl ether, vinylpyrrolidone, allyl ester and allyl sulfide.

The 21^(st) aspect of the present invention provides the polymerproduced by the polymerization process of one of the 11^(th) to 20^(th)aspects.

The 22^(nd) aspect of the present invention provides the polymer of the21^(st) aspect, whose molecular weight is controlled by areaction-controlling agent; the 23^(rd) aspect of the present inventionprovides the polymer of the 21^(st) aspect, wherein an anti-oxidant isincorporated in the polymerization system.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in detail below.

1. Organometallic Compound

The first aspect of the present invention is an organometallic compound(hereinafter referred to as First Organometallic Compound) containingruthenium or osmium and silicon, represented by the general formula (1):

Wherein, M is ruthenium or osmium; R₁ to R₄ are each hydrogen atom, analkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbonatoms, aryl group of 6 to 20 carbon atoms, carboxyl group of 2 to 20carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms,alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20carbon atoms, alkylsilyl group of 2 to 20 carbon atoms, arylsilyl groupof 2 to 20 carbon atoms or ferrocene derivative, which may be the sameor different and substituted, as required, with a phenyl groupsubstituted with an alkyl group of 1 to 5 carbon atoms, halogen atom oralkoxy group of 1 to 5 carbon atoms; X₁ and X₂ are each an anionicligand, which may be the same or different; and L₁ and L₂ are each aneutral electron donor, which may be the same or different; where 2 or 3of X₁, X₂, L₁ and L₂ may together form a multidentate, chelated ligand.

The substituent R₁ is preferably the one other than hydrogen atom in theabove range, viewed from stability and catalytic activity of theorganometallic compound. In other words, catalytic activity of anorganometallic compound, when used for a metathesis reaction, is greatlyaffected by electron density of the central metal, increasing electrondensity improving its affinity for the reaction matrix and hencereaction activity. Therefore, the substituent is preferably other thanhydrogen atom, viewed from catalytic activity. An organometalliccompound has greatly improved stability as its bulk density increases.Therefore, the substituent is preferably other than hydrogen atom, alsoviewed from stability.

More specifically, the substituents represented by R₁ preferable forimproving electron density of the metal include phenyl, t-butyl,n-butyl, n-propyl, isopropyl, ethyl and methyl group. A phenyl groupsubstituted with an electron-donating group (e.g., alkyl or alkoxygroup) is more preferable, because it can improve electron density ofthe metal more efficiently. These groups include tolyl and anisyl group.

The other preferable substituents represented by R₁ includemethoxymethyl, ferrocenyl and trimethylsilyl (TMS) group, because theypush electrons onto the metal.

Each of the substituents R₂ to R₄ is preferably selected from the groupconsisting of methyl, ethyl, isopropyl, t-butyl, cyclohexyl and phenylgroup, because they can be bonded to a silicon atom while overlappingeach other.

When R₁ is hydrogen atom, in particular, the organometallic compoundpreferably contains phenyl, isopropyl, t-butyl group or the like,because of its effect of stabilizing the compound. When R₁ is other thanhydrogen atom, on the other hand, even methyl group as each of thesubstituents R₂ to R₄ can allow the metathesis reaction to proceed,because the organometallic compound can be stably present.

L₁ and L₂ are each a neutral electron donor, as described earlier, andpreferably a phosphorus -based ligand. The preferable phosphorus-basedligands include a phosphine represented by the formula PR₉R₁₀R₁₁,wherein R₉, R₁₀ and R₁₁ are each an alkyl group of 1 to 20 carbon atomsor aryl group of 6 to 20 carbon atoms, preferably methyl, ethyl,isopropyl, t-butyl, cyclohexyl, phenyl or substituted phenyl. R₉, R₁₀and R₁₁ may be the same or different.

More specifically, L₁ and L₂ may be each —P(cyclohexyl)₃, —P(phenyl)₃ or—P(isopropyl)₃.

X₁ and X₂ in the general formula (1) may be selected from any anionicligands, preferably Cl or Br, the former being more preferable.

First Organometallic Compound of the present invention can be producedby various processes. One of the processes produces the objectiveorganometallic compound represented by the formula (1) by theligand-exchanging reaction according to the reaction (i) between aruthenium or osmium complex precursor as one of the starting compoundsand neutral electron-donating ligand compound as the other startingcompound, each starting compound being produced by a known process.

The reaction (i) is effected at a low temperature (e.g., −78° C.) in anorganic solvent (e.g., dichloromethane), because a diazomethanederivative as one of the starting compounds is a very unstable compoundwith nitrogen easily eliminated to form a carbene species, which reactswith the metal.

The fifth aspect of the present invention, on the other hand, is anorganometallic compound (hereinafter referred to as SecondOrganometallic Compound) containing ruthenium or osmium and silicon,represented by the general formula (2):

Wherein, M is ruthenium or osmium; R₅ to R₈ are each hydrogen atom, analkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbonatoms, aryl group of 6 to 20 carbon atoms, carboxyl group of 2 to 20carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms,alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20carbon atoms, alkylsilyl group of 2 to 20 carbon atoms, arylsilyl groupof 2 to 20 carbon atoms or ferrocene derivative, which may be the sameor different and substituted, as required, with a phenyl groupsubstituted with an alkyl group of 1 to 5 carbon atoms, halogen atom oralkoxy group of 1 to 5 carbon atoms; X₃ and X₄ are each an anionicligand, which may be the same or different; and L₃ and L₄ are each aneutral electron donor, which may be the same or different; where 2 or 3of X₃, X₄, L₃ and L₄ may together form a multidentate, chelated ligand.

The substituent R₅ is preferably the one other than hydrogen atom in theabove range, viewed from stability and catalytic activity of theorganometallic compound. In other words, catalytic activity of anorganometallic compound, when used for a metathesis reaction, is greatlyaffected by electron density of the central metal, increasing electrondensity improving its affinity for the reaction matrix and hencereaction activity. Therefore, the substituent R₅ is preferably otherthan hydrogen atom, viewed from catalytic activity. An organometalliccompound has greatly improved stability as its bulk density increases.Therefore, the substituent is preferably other than hydrogen atom, alsoviewed from stability.

More specifically, the substituents represented by R₅ preferable forimproving electron density of the metal include phenyl, t-butyl,n-butyl, n-propyl, isopropyl, ethyl and methyl group. A phenyl groupsubstituted with an electron-donating group (e.g., alkyl or alkoxygroup) is more preferable, because it can improve electron density ofthe metal more efficiently. These groups include tolyl and anisyl group.

The other preferable substituents represented by R₅ includemethoxymethyl, ferrocenyl and trimethylsilyl (TMS) group, because theypush electrons onto the metal.

Each of the substituents R₆ to R₈ is preferably selected from the groupconsisting of methyl, ethyl, isopropyl, t-butyl, cyclohexyl and phenylgroup, because they can be bonded to a silicon atom while overlappingeach other.

When R₅ is hydrogen atom, in particular, the organometallic compoundpreferably contains phenyl, isopropyl, t-butyl group or the like,because of its effect of stabilizing the compound. When R₅ is other thanhydrogen atom, on the other hand, even methyl group as each of thesubstituents R₆ to R₈ can allow the metathesis reaction to proceed,because the organometallic compound can be stably present.

L₃ and L₄ are each a neutral electron donor, as described earlier, andpreferably a phosphorus-based ligand. The preferable phosphorus-basedligands include a phosphine represented by the formula PR₁₂R₁₃R₁₄,wherein R₁₂, R₁₃ and R₁₄ are each an alkyl group of 1 to 20 carbon atomsor aryl group of 6 to 20 carbon atoms, preferably methyl, ethyl,isopropyl, t-butyl, cyclohexyl, phenyl or substituted phenyl. They maybe the same or different.

More specifically, L₃ and L₄ may be each —P(cyclohexyl)₃, —P(phenyl)₃ or—P(isopropyl)₃, among others.

X₃ and X₄ in the general formula (2) may be optionally selected fromanionic ligands, preferably Cl or Br, the former being more preferable.

Chem. Lett., 1998, page 67, illustrates some organometallic compoundscorresponding to the general formula (2) and describes the metathesispolymerization which uses these compounds. However, this article merelyscientifically predicts the compounds, considered to be intermediatelyformed in the reaction system, and does not isolate or confirm thecomplexes. These compounds are apparently different from theorganometallic compound of the present invention, which is isolated toconfirm its structure chemically and physicochemically, and itsmetathesis catalyst function.

Second Organometallic Compound of the present invention can be producedby various processes. One of the processes produces the objectiveorganometallic compound represented by the formula (2) by theligand-exchanging reaction and rearrangement according to the reaction(ii) or (iii) between a ruthenium or osmium complex precursor as one ofthe starting compounds and neutral electron-donating ligand compound asthe other starting compound, each starting compound being produced by aknown process.

Each of the reactions (ii) and (iii) proceeds easily under conditionsof, e.g., at normal temperature to 80° C. in an organic solvent, e.g.,dichloromethane, dichloroethane, toluene or THF.

2. Metathesis Reaction Catalyst

Each of First and Second Organometallic Compounds of the presentinvention (hereinafter sometimes referred to generically as theorganometallic compound of the present invention) can be suitably usedfor the metathesis reaction.

The metathesis reactions include a structural change within the samemonomer having an unsaturated bond, cross-metathesis reaction betweenmonomers having an unsaturated bond, and metathesis polymerization. Themetathesis polymerization may be ring-opening or non-cyclic type.

Second Organometallic Compound of the present invention is more suitablyused than First Organometallic Compound, because of its better reactioncontrollability.

The organometallic compound of the present invention, when used for themetathesis reaction, may be incorporated with a reaction-adjusting agentin the reaction process. Use of such an agent can control reaction rate.The agent can accelerate or decelerate the metathesis reaction, when itstype and content are adequately set. The reaction-adjusting agent is notlimited. However, an acidic component is particularly preferable, whenthe reaction is to be accelerated.

The acid component useful for the present invention as thereaction-adjusting agent is not limited. A so-called Brosnted acid(protonic acid) can be used. Examples of these acids includehydrochloric, sulfuric, nitric, acetic and formic acid, and ammoniumchloride in the form of aqueous solution. The acid component maydecompose the organometallic compound itself, depending on type of theorganometallic compound or metathesis-reactive monomer used, todeactivate the catalyst. It is therefore preferable to incorporate aweak acid of very low acidity selected from the above acid components. Achlorine-based solvent may be also used as a solvent of very lowacidity. Methylene chloride, for example, may be used as thechlorine-based solvent. Moreover, the reaction system can be kept weaklyacidic in the presence of silica gel, which is used for columnchromatography.

Content of the reaction-adjusting agent is not limited. However, it isincorporated normally at 10 to {fraction (1/10,000)} equivalents perequivalent of the organometallic compound of the present inventionworking as the metathesis reaction catalyst, preferably 1 to {fraction(1/100)} equivalents.

The organometallic compound of the present invention, when used for themetathesis reaction, may be incorporated with a reaction-controllingagent in the reaction process. Use of such an agent can controlmolecular weight of the product polymer. It can freely control themolecular weight, when its type and content (its ratio to the monomer)are adequately set. The reaction-controlling agent is preferably acompound having a metathesis-reactive unsaturated bond, in particular acompound containing a hetero element.

The compound having a metathesis-reactive unsaturated bond, useful forthe present as the reaction-controlling agent, is not limited. Examplesof these compounds include vinyl ester, vinyl sulfide, vinyl ether,vinyl pyrrolidone, allyl ester and allyl sulfide.

Content of the reaction-controlling agent is not limited, and variesdepending on molecular weight of the objective polymer. However, it isincorporated normally at ½ to {fraction (1/10,000)} equivalents perequivalent of the metathesis-reactive monomer, preferably ½ to {fraction(1/1000)} equivalents.

The organometallic compound of the present invention is more stable inair, stable to a functional or polar group, and resistant to heat thanthe conventional metathesis reaction catalyst. When used for metathesispolymerization, it can greatly reduce quantity of the monomer remainingafter the polymerization process with the above favorablecharacteristics.

The metathesis process proceeding in the presence of the organometalliccompound of the present invention may be effected in a solvent. Anorganic solvent which can dissolve the metathesis-reactive monomer ispreferable, when the reaction is effected in a homogeneous system.Examples of these solvents include toluene, benzene, chloroform, hexaneand xylene. The reaction may be effected in a heterogeneous system. Asolvent which little dissolves the metathesis-reactive monomer, e.g.,water, can be also used, because the organometallic compound of thepresent invention is stable to hydrogen or oxygen. Moreover, suspensionor dispersion polymerization can be adopted in the presence of adispersion stabilizer or the like.

The reaction conditions of the metathesis reaction effected in thepresence of the organometallic compound of the present invention aredescribed. Content of the organometallic compound of the presentinvention is preferably ⅕ to {fraction (1/500,000)} equivalents perequivalent of the whole metathesis-reactive monomer(s). At above ⅕equivalents, the polymer product may not have a sufficient molecularweight, when it is used for a polymerization process. At below {fraction(1/500,000)} equivalents, on the other hand, the reaction may notproceed at a sufficient rate, and hence is undesirable. More preferably{fraction (1/30)} to {fraction (1/200,000)} equivalents per equivalentof the whole metathesis-reactive monomer(s).

Reaction temperature of the metathesis reaction effected in the presenceof the organometallic compound of the present invention varies dependingon melting point and boiling point of the compounds used for theprocess, e.g., metathesis-reactive monomer, solvent, reaction-adjustingagent and reaction-controlling agent. However, it is preferably −30 to170° C., more preferably −30 to 150° C.

3. Metathesis Polymerization Process and Polymer

The organometallic compound of the present invention is suitable as acatalyst for metathesis polymerization, ring-opening or non-cyclic, asdescribed earlier. When the organometallic compound of the presentinvention is used for ring-opening metathesis polymerization, themonomer for the polymerization is not limited. The useful cyclic,unsaturated compounds include polycyclic, unsaturated compounds, e.g.,norbornene and its derivatives and dicyclopentadiene and itsderivatives, and cyclobutene, cyclohexene, cyclooctene andcyclooctadiene.

For norbornene and its derivatives, the preferable ones for the presentinvention are polycyclic norbornene-based monomers of bicyclic or higherstructure. Such a monomer gives a norbornene-based polymer of highthermal deformation temperature.

The bicyclic norbornene-based monomer is not limited. Some of theexamples include 2-norbornene, 5-methyl-2-norbornene,5-ethylidene-2-norbornene and 5-phenyl norbornene.

The polycyclic norbornene-based monomer of tricyclic or higher structureis also not limited. Some of the examples are tricyclic ones, e.g.,dicyclopentadiene (DCPD) and dihydroxypentadiene; tetracyclic ones,e.g., tetracyclododecene; pentacyclic ones, e.g., tricyclopentadiene;heptacyclic ones, e.g., tetracyclopentadiene; alkyl-substitutedpolycyclic monomers, e.g., methyl-, ethyl-, propyl- andbutyl-substituted ones; alkylidene-substututed ones, e.g.,ethylidene-substituted ones; and aryl-substituted ones, e.g., phenyl-,tolyl- and naphthyl-substituted ones. These norbornene-based monomersmay be used either individually or in combination. Of these, morepreferable ones are crosslinkable monomers of dicyclopentadiene andtricyclopentadiene, viewed from their availability, reactivity, heatresistance and so on, because they are excellent in reaction ratecontrollability and high reactivity.

Moreover, the organometallic compound of the present invention can beused for metathesis polymerization of a monomer containing a functionalgroup. The functional groups for these monomers are widely varying, andmay be polar or non-polar. They include hydroxyl, carboxyl, amino,ester, acetoxy, alkoxy, halogen, carbonyl, mercapto, epoxy, silyl,oxazoline, sulfonate, maleimide, azlactone and vinyl, to begin with.

When the organometallic compound of the present invention is used formetathesis polymerization, polymerization of a norbornene-based monomeris one example in which high heat resistance as one of thecharacteristics of the organometallic compound is fully utilized. Theconventional polymerization catalyst, when used for polymerization of anorbornene-based monomer, will be partly deactivated due to a largequantity of heat released by the exothermic reaction, unless it is inthe form of diluted solution. On the other hand, the organometalliccompound of the present invention loses the catalytic activity to alesser extent, and leaves the unreacted monomer also to a lesser extentafter completion of the polymerization process. These favorable effectswill be more noted when it is used for polymerization ofdicyclopentadiene as the monomer.

Polymerization of a norbornene-based monomer as a metathesis-reactivemonomer is effected preferably at −20 to 220° C. At below −20° C., anorbornene-based monomer may be too low in fluidity to smoothlyincorporate the organometallic compound of the present invention. On theother hand, polymerization temperature of above 220° C. is undesirable,because it may deactivate the metathesis catalyst. More preferabletemperature is 10 to 200° C., still more preferably 20 to 180° C., mostpreferably 60 to 180° C.

The metathesis polymerization process of the present invention iseffected preferably in an inert gas atmosphere, but may be effected inair when the stable catalyst is used.

The polymer produced by the metathesis reaction, having a double bond,may be deteriorated by oxygen in air. The polymerization system may beincorporated with an anti-oxidant to prevent the deterioration.

The anti-oxidant useful for the present invention is not limited, solong as it is harmless to the metathesis polymerization reaction. Thepreferable ones include pentaerythritol-tetrakis[3-(3-di-t-butyl-4-hydroxyphenyl)propionate],1,3,5-trimethyl-2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)benzene,2,6-di-t-butyl-4-methyl phenol,tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate and1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate.

Content of the anti-oxidant is not limited. However, it is incorporatednormally at 20 to 0.01% by weight of the whole composition in thepolymerization system, preferably 5 to 0.1% by weight.

The organometallic compound catalyst of the present invention hasanother advantage, when used for polymerization of a monomer, e.g.,DCPD, to produce a thermosetting resin which needs reaction molding,because it can give a curing speed more suitable for molding processthan does the conventional ruthenium-based catalyst, with the resultthat addition of a third component, e.g., retardant, is not essential.

The polymer or its composition produced by polymerizing ametathesis-reactive monomer, e.g., norbornene, in the presence of theorganometallic compound catalyst of the present invention is excellentin adhesion, resistance to heat, resistance to chemicals and so on, andcan be used for various areas which need these characteristics, e.g.,electrical/electronic parts, baths and combined purification tanks.

The metathesis-polymerized polymer or its composition produced in thepresence of a reaction-controlling agent in addition to ametathesis-reactive monomer, e.g., norbornene, can be used for stillwider areas which need these characteristics (adhesion, resistance toheat, resistance to chemicals and so on) than the one produced in theabsence of such an agent, because its degree of polymerization can befreely controlled by adequately selecting type and content of the agent.

The metathesis-polymerized polymer or its composition produced in thepresence of a reaction-controlling agent can be also used asfunction-donating agents, e.g., plasticizer and molding aid, because ofits controlled molecular weight.

The metathesis-polymerized polymer produced in the presence of theorganometallic compound of the present invention can be designed forvarious properties, e.g., melting and glass transition temperature, bycopolymerizing two or more types of metathesis-reactive monomers, tostill widen its applicable areas as function-donating agents.

EXAMPLES AND COMPARATIVE EXAMPLES

The present invention is described more specifically by EXAMPLES.However, it should be understood that the present invention is notlimited to EXAMPLES.

Examples 1 to 15

In EXAMPLES 1 to 15, the organometallic compounds were synthesized bythe reaction (ii) or (iii) to have the structure represented by one ofthe formulae (3) to (17). Table 1 summarizes the organometallic compoundstructures prepared in EXAMPLES, and metallic elements, ligands,substituents and the like in the general formula (2).

In EXAMPLE 1, the organometallic compounds represented by the formula(3) were synthesized by the reactions (ii) and (iii). These compoundswere found to be identical to each other, as discussed later in Sections(A) and (B).

The objective organometallic compounds were prepared in EXAMPLES 2 to 13and EXAMPLE 15 by the reaction (ii) or (iii) in the same manner as inEXAMPLE 1 except that the starting material was changed. The reaction(iii) involves a disadvantage in that a sterically bulky ligand, e.g.,N,N′-dimethylimidazolium carbene, is difficult to introduce. Bycontrast, the reaction (ii) can easily introduce such a ligand.Accordingly, the organometallic compound was prepared by the reaction(ii) in EXAMPLE 14.

Each of these organometallic compounds was identified by, e.g., theelementary and NMR spectral analysis. The analysis results are describedtogether after Table 1.

The NMR spectral analysis was conducted using a Varian Mercury 300spectrometer under the conditions of chemical Shifts δ (ppm), 25° C.,and standard of 1H-NMR: SiMe₄, 31P{1H} NMR: 85% H₃PO₄.

(A) Synthesis of the Organometallic Compound Represented by the Formula(3) (by the Reaction (ii))

-   (A-1) A mixture of 0.006 mols of Ru(p-cymene)Cl₂ to which 0.012 mols    of tricyclohexylphosphine and 0.06 mols of acetonitrile were added    was heated in the presence of 20 g of toluene in a 100 mL flask in a    flow of nitrogen at 80° C. for 6 hours for the reactions. On    completion of the reaction process, the produced precipitates were    recovered and washed to isolate the complex (yield: 78%). The    analysis indicated that it had a structure represented by the    formula (a):

1H-NMR (CDCl₃) δ=1.25, 1.71 to 2.18, 2.54 (each m, 66H) 2.39 (s, 6H,CH₃CN): 31P {1H} NMR (CDCl₃) δ=11.28(s). Elementary analysis:C40H72Cl2N2P2Ru: Calculated composition C: 58.95%, H: 8.91% and N:3.44%, Observed composition C: 59.11%, H: 9.03% and N: 3.33%

-   (A-2) A mixture of 0.006 mmols of the organometallic compound    represented by the formula (a) to which 0.009 mols of    1-trimethylsilylhexyl was added was heated in the presence of    dichloroethane as a solvent at 60° C. for 1 hour. The reaction    effluent solution was treated to remove the solvent, and the    resultant solids were recrystallized in a THF/ethanol system, to    isolate the complex (yield: 78%). The analysis indicated that it had    a structure represented by the formula (3), described later.

1H-NMR (CDCl₃) δ=0.10 (s, 9H, —SiMe₃), 0.85 (t, J=6.9 Hz, 3H,—C₃H₆—CH₃), 1.25, 1.56 to 1.79, 2.06 (each m, 60H, PCy₃, and 4H,—CH₃—C₂H₄—CH₃) 2.22 (bt, 2H, —CH₂—C₃H₇) 2.61 (bt, 6H, PCy₃): 31P {1H}NMR (CDCl₃) δ=19.90(s), Elementary analysis: C45H84Cl2P2SiRu: Calculatedcomposition C: 60.92% and H: 9.54%, Observed composition C: 60.62% andH: 9.50%

(B) Synthesis of the Organometallic Compound Represented by the Formula(3) (by the Reaction (iii))

A mixture of 1.87 g (0.006 mols) of Ru(p-cymene)Cl₂ to which 3.42 g(0.012 mols) of tricyclohexylphosphine and 1.67 g (0.009 mols) oftriisopropylsilylacetylene were added was heated in the presence of 20 gof toluene in a 100 mL flask in a flow of nitrogen at 80° C. for 24hours for the reactions. On completion of the reaction process, toluenewas distilled off under a vacuum, and the resultant solids wererecrystallized in a THF/ethanol system, to synthesize 4.8 g of theorganometallic compound (yield: 75%). The analysis indicated that it hada structure represented by the formula (3), described later. It had acomposition of C: 62.01% and H: 9.59% (theoretical composition is C:61.08% and H: 9.69%), as determined by the elementary analysis.

TABLE 1 M L₃ L₄ X₃ X₄ R₅ R₆ R₇ R₈ formula EXAMPLE 1 Ru PCy₃ PCy₃ Cl ClnBu Me Me Me 3 EXAMPLE 2 Ru PCy₃ PCy₃ Cl Cl Ph Me Me Me 4 EXAMPLE 3 RuPCy₃ PCy₃ Cl Cl nPr Me Me Me 5 EXAMPLE 4 Ru PCy₃ PCy₃ Cl Cl Me Me Me Me6 EXAMPLE 5 Ru PCy₃ PCy₃ Cl Cl SiMe₃ Me Me Me 7 EXAMPLE 6 Ru PCy₃ PCy₃Cl Cl p-MeOPh Me Me Me 8 EXAMPLE 7 Ru PCy₃ PCy₃ Cl Cl CH₂OMe Me Me Me 9EXAMPLE 8 Ru PCy₃ PCy₃ Cl Cl SPh Me Me Me 10 EXAMPLE 9 Ru PCy₃ PCy₃ ClCl 1-cyclohexenyl Me Me Me 11 EXAMPLE 10 Ru PCy₃ PCy₃ Cl Cl COOH Me MeMe 12 EXAMPLE 11 Ru PCy₃ PCy₃ Cl Cl H iPr iPr iPr 13 EXAMPLE 12 Ru PCy₃PCy₃ Cl Cl H tBu Me Me 14 EXAMPLE 13 Ru PCy₃ PCy₃ Cl Cl H Ph Ph Me 15EXAMPLE 14 Ru Imes PCy₃ Cl Cl Ph Me Me Me 16 EXAMPLE 15 Os PCy₃ PCy₃ ClCl Ph Me Me Me 17

In Table 1, IMes introduced as L₃ in EXAMPLE 14 is a ligand representedby the formula (18):

The organometallic compounds given in Table 1 have a structurerepresented by one of the formulae (3) to (17).

The organometallic compounds given in Table 1, represented by one of theformulae (3) to (17), had the following NMR spectral and elementaryanalysis results:

Organometallic Compound Represented by the Formula (4)

1H-NMR (CDCl₃) δ=0.29 (s, 9H, —SiMe₃), 1.20, 1.49 to 1.82, 2.09, 2.65(each m, 66H, PCy₃), 7.09 to 7.28 (each m, 5H, Ph): 31P {1H} NMR (CDCl₃)δ=20.60(s). Elementary analysis: C47H80Cl2P2SiRu: Calculated compositionC: 62.23% and H: 8.89%, Observed composition C: 61.97% and H: 8.78%

Organometallic Compound Represented by the Formula (5)

1H—NMR (CDCl₃) δ=0.10 (s, 9H, —SiMe₃), 0.84 (t, J=7.2 Hz, 3H,—C₂H₄—CH₃), 1.25, 1.56 to 1.79, 2.06 (each m, 60H, PCy₃, and 2H,—CH₂—CH₂—CH₃) 2.20(bt,2H, —CH₂—C₂H₅) 2.61 (bt, 6H, PCy₃): 31P {1H} NMR(CDCl₃) δ=19.84(s). Elementary analysis: C44H82Cl2P2SiRu: Calculatedcomposition C: 60.52% and H: 9.47%, Observed composition C: 60.22% andH: 9.42%

Organometallic Compound Represented by the Formula (6)

1H-NMR (CDCl₃) δ=0.10 (s, 9H, —SiMe₃), 1.25, 1.56 to 1.79, 2.06 (each m,60H) 2.20 (s, 3H, —CH₃) 2.61 (bt, 6H, PCy₃): 31P {1H} NMR (Toluene)δ=20.93(s). Elementary analysis: C42H78Cl2P2SiRu: Calculated compositionC: 59.69% and H: 9.30%, Observed composition C: 59.39% and H: 9.26%

Organometallic Compound Represented by the Formula (7)

1H-NMR (CDCl₃) δ=0.17 (s, 18H, —SiMe₃), 1.25, 1.59 to 1.78, 2.09, 2.68(each m, 66H, PCy₃): 31P {1H} NMR (CDCl₃) δ=20.97(s). Elementaryanalysis: C44H84Cl2P2Si2Ru: Calculated composition C: 58.51% and H:9.37%, Observed composition C: 58.41% and H: 9.34%

Organometallic Compound Represented by the Formula (8)

1H-NMR (CDCl₃) δ=0.27 (s, 9H, —SiMe₃), 1.20, 1.60 to 1.68, 2.06, 2.65(each m, 66H, PCy₃): 3.74 (s, 3H, —OMe₃), 6.71, 7.14 (each d, J=8.4 Hz,2H, C₆H₄): 31P {1H} NMR (CDCl₃) δ=20.09(s). Elementary analysis:C48H82Cl2P2OSiRu: Calculated composition C: 61.51% and H: 8.82%,Observed composition C: 61.31% and H: 8.78%

Organometallic Compound Represented by the Formula (9)

1H-NMR (CDCl₃) δ=0.27 (s, 9H, —SiMe₃), 1.20, 1.60 to 1.68, 2.06, 2.65(each m, 66H, PCy₃): 3.50 (s, 3H, —OMe), 4.01 (s, 2H, —CH₂—O): 31P {1H}NMR (CDCl₃) δ=20.89(s). Elementary analysis: C41H74Cl2P2OSiRu:Calculated composition C: 58.27% and H: 8.83%, Observed composition C:58.11% and H: 8.79%

Organometallic Compound Represented by the Formula (10)

1H-NMR (CDCl₃) δ=0.29 (s, 9H, —SiMe₃), 1.20, 1.49 to 1.82, 2.09, 2.65(each m, 66H, PCy₃), 7.09 to 7.28 (each m, 5H, Ph): 31P {1H} NMR (CDCl₃)δ=20.60(s). Elementary analysis: C47H80Cl2P2SiRu: Calculated compositionC: 62.23% and H: 8.89%, Observed composition C: 61.97% and H: 8.78%

Organometallic Compound Represented by the Formula (11)

1H-NMR (CDCl₃) δ=0.30 (s, 9H, —SiMe₃), 1.20, 1.49 to 1.82, 2.05 to 2.10,2.65 (each m, 74H, PCy₃ and >C═CH—(CH₂)₄—), 6.21 (bt, 1H, >C═CH—): 31P{1H} NMR (CDCl₃) δ=19.10(s). Elementary analysis: C47H84Cl2P2SiRu:Calculated composition C: 61.95% and H: 9.29%, Observed composition C:61.77% and H: 8.98%

Organometallic Compound Represented by the Formula (12)

1H-NMR (CDCl₃) δ=0.32 (s, 9H, —SiMe₃), 1.15, 1.52 to 1.79, 2.10, 2.68(each m, 66H, PCy₃): 31P {1H} NMR (CDCl₃) δ=21.60(s). Elementaryanalysis: C42H76Cl2O2P2SiRu: Calculated composition C: 57.64% and H:8.75%, Observed composition C: 57.27% and H: 8.88%

Organometallic Compound Represented by the Formula (13)

1H-NMR (CDCl₃) δ=1.02 (d, J=2.4 Hz, 18H, —CH(CH)₂), 1.23, 1.57 to 1.78,2.08, 2.68 (each m, 66H, PCy₃, and 3H, —CH(CH₃)₂), 2.81 (t, ⁴J_(PH)=3Hz, 1H, ═C═CH): 31P {1H} NMR (CDCl₃) δ=21.42(s). Elementary analysis:C47H88Cl2P2SiRu: Calculated composition C: 61.68% and H: 9.69%, Observedcomposition C: 61.56% and H: 9.64%

Organometallic Compound Represented by the Formula (14)

1H-NMR (CDCl₃) δ=0.09 (s, 6H, —SiMe₂), 0.81 (s, 9H, —SitBu), 1.25, 1.57to 1.79, 2.09, 2.68 (each m, 66H, —PCy₃), 2.90 (t, ⁴J_(PH)=3 Hz, 1H,═C═CH): 31P {1H} NMR (CDCl₃) δ=21.46(s). Elementary analysis:C44H82Cl2P2SiRu: Calculated composition C: 60.52% and H: 9.47%, Observedcomposition C: 60.75% and H: 9.55%

Organometallic Compound Represented by the Formula (15)

1H-NMR (CDCl₃) δ=0.68 (s, 3H, —SiMe), 1.92, 1.50 to 1.69, 2.08, 2.64(each m, 66H, —PCy₃), 3.44 (t, ⁴J_(PH)=3 Hz, 1H, ═C═CH): 7.24 to 7.32,7.48 to 7.51 (each m, 10H, —Ph): 31P {1H} NMR (CDCl₃) δ=22.07(s).Elementary analysis: C51H80Cl2P2SiRu: Calculated composition C: 64.13%and H: 8.44%, Observed composition C: 63.92% and H: 8.40%

Organometallic Compound Represented by the Formula (16)

1H-NMR (CDCl₃) δ=0.29 (s, 6H, —SiMe₃), 1.20, 1.49 to 1.83, 2.11, 2.64(each m, 33H, PCy₃), 1.82 (s, 6H, p-Me-Mesythyl), 2.25 (s, 12H,o-Me-Mesythyl) 6.22 (s, 2H, ═CH—) 6.99 (s, 4H, m-H-Mesythyl) 7.11 to7.38 (each m, 5H, Ph): 31P {1H} NMR (CDCl₃) δ=33.60(s). Elementaryanalysis: C50H71Cl2N2PSiRu: Calculated composition C: 64.49%, H: 7.68%and N: 3.01%, Observed composition C: 64.77%, H: 7.78% and N: 3.05%

Organometallic Compound Represented by the Formula (17)

1H-NMR (CDCl₃) δ=0.25 (s, 9H, —SiMe₃), 1.20, 1.49 to 1.90, 2.05, 2.70(each m, 66H, PCy₃), 7.05 to 7.32 (each m, 5H, Ph): 31P {1H} NMR (CDCl₃)δ=22.60(s). Elementary analysis: C47H80Cl2P2SiOs: Calculated compositionC: 56.66% and H: 8.09%, Observed composition C: 56.88% and H: 8.11%

Example 16

The organometallic compound having a structure represented by theformula (19) was synthesized in EXAMPLE 16 by the reaction (i).

0.006 mols of RuCl₂(PPh₃)₃ was reacted with 0.006 mols oftrimethylsilyldiazomethane in 20 mL of methylene chloride at −78° C. for5 minutes. Then, the reaction effluent solution was heated to roomtemperature, to which 0.0132 mols of tricyclohexylphosphine was added,and they were reacted with each other for 30 minutes. On completion ofthe reaction process, the effluent solution was treated to distill offthe solvent under a vacuum, and the resultant solids were recrystallizedin a methylene chloride/methanol system, to isolate the complex (yield:75%). The analysis indicated that it had a structure represented by theformula (19).

1H-NMR (CDCl₃) δ=0.20 (s, 9H, —SiMe₃), 1.18, 1.49 to 1.72, 2.64 (each m,66H, PCy₃), 19.8 (s, Ru═CH, 1H, Ph): 31P {1H} NMR (CDCl₃) δ=19.60(s).Elementary analysis: C40H76Cl2P2SiRu: Calculated composition C: 58.65%and H: 9.35%, Observed composition C: 58.60% and H: 9.15%

Table 2 summarizes the organometallic compound structure prepared inEXAMPLE 16, and metallic element, ligands, substituents and the like inthe general formula (1).

TABLE 2 M L₁ L₂ X₁ X₂ R₁ R₂ R₃ R₄ formula EXAMPLE Ru PCy₃ PCy₃ Cl Cl nBuMe Me Me 19 16

Examples 17 to 19

The metathesis polymerization of DCPD was effected using theorganometallic compound of the present invention in each of EXAMPLES 17to 19, to evaluate the resultant polymer.

0.1 mmols ({fraction (1/10,000)} mols of DCPD) of the organometalliccompound represented by the formulae (3), (4) or (13) was dissolved in0.5 g of toluene, to which 132 g of DCPD was added. The mixture was thenpoured into a container via a 4 mm thick spacer, where it was kept at80° C. for 1 hour, and then left at 120° C. for 1 hour, to prepare thepolymer as the sample for property evaluation. It was measured by thedynamic viscoelasticity testing method (stretching method (n=1) using aviscoelasticity spectrometer in accordance with JIS K-7198), todetermine temperature at which the tan δ value attained a maximum. Thetemperature level was used as glass transition temperature of the resin.

The sample (0.5 g) was taken from the polymer produced, and put in a 10ml measuring flask, to which toluene was added to a given level. Themixture was left at room temperature for 20 hours, and the residualmonomer was extracted and filtered by a 0.2 μm filter, to prepare thetest piece. The residual monomer was measured by the followingquantitative analysis.

[Quantitative Analysis]

The calibration solutions of 0.01, 0.1 and 0.5% (weight/volume %) ofDCPD were prepared, and each was diluted with toluene and quantitativelyanalyzed by the absolute calibration line method (least square method).Each calibration solution was analyzed by gas chromatography under thefollowing conditions. Residual monomer content was determined by thefollowing formula:Residual monomer content (% by weight)=(GC-detected quantity(weight/volume %)×10 mL)/sample weight (g)

-   -   Analyzer: Gas chromatograph (Shimadzu Corp.'s GC14A)    -   DCPD-analyzing column and temperature    -   Column: THERMON-3000, 5% SHINCARBON60/80 mesh, 2.1M,        -   I.D.: 3.2 mm    -   Temperature:        -   Column: 100° C. (1 minute)˜(10° C./minute)˜150° C. (1            minute)        -   Inlet port: 200° C.,        -   Detector section: 200° C.    -   Carrier gas:        -   He: 60 kPa, Combustion gases: Air 60 kPa, H₂ 60 kPa        -   Carrier flow rate: He 55 cm³/minute

Table 3, described later, summarizes the tan δ peak temperature levelsand residual monomer contents, determined by the above procedures.

Example 20

91 mg ({fraction (1/10,000)} mols of DCPD) of the ruthenium complex ofthe present invention, represented by the formula (4), was dissolved in0.5 g of toluene, to which 132 g of DCPD and then 1 ml of 0.1Nhydrochloric acid were added. The mixed solution was stirred at 40° C.for 5 minutes, and then poured into a container via a 4 mm thick spacer,where it was kept at 80° C. for 1 hour, and then left at 120° C. for 1hour, to prepare the sample for property evaluation. It was measured inthe same manner as in EXAMPLES 17 to 19. Table 3, described later,summarizes the measured tan δ peak temperature levels and residualmonomer contents.

Comparative Example 1

An attempt was made to synthesize a polymer using the organometalliccompound represented by the formula (20), described in Japanese PatentLaid-Open No.11-510807, in the same manner as in EXAMPLES 17 to 19, andto evaluate product properties. However, the polymerization reactionproceeded too fast to obtain the sample for tan δ peak evaluation. Onlythe residual monomer content is reported for this sample in Table 3,described later.

Comparative Examples 2 to 3

A polymer was synthesized and evaluated in each of COMPARATIVE EXAMPLES2 to 3 using the organometallic compound, represented by the formula(21) or (22) and described in Japanese Patent Laid-Open No.11-510807, inthe same manner as in EXAMPLES 17 to 19. Table 3, described later,summarizes the measured tan δ peak temperature levels and residualmonomer contents.

Comparative Example 4

A polymer was synthesized and evaluated in COMPARATIVE EXAMPLE 4 usingthe organometallic compound, represented by the formula (23) anddescribed in Organometallics, 1998, 17, 5190, in the same manner as inEXAMPLES 17 to 19. Table 3, described later, summarizes the measured tanδ peak temperature level and residual monomer content.

TABLE 3 Com- Residual monomer plex Tan δ content EXAMPLE 17 3 154° C.0.30% EXAMPLE 18 4 156° C. 0.30% EXAMPLE 19 13 157° C. 0.20% EXAMPLE 204 158° C. 0.10% COMPARATIVE EXAMPLE 1 20 — 2.50% COMPARATIVE EXAMPLE 221 139° C. 1.50% COMPARATIVE EXAMPLE 3 22 133° C. 2.30% COMPARATIVEEXAMPLE 4 23 141° C. 1.80%

It is confirmed, as shown in Table 3, that the metathesis reaction inthe presence of the organometallic compound of the present inventiongives a polymer of higher tan δ peak temperature than the one in thepresence of the conventional metathesis catalyst. It is also confirmedthat it leaves the residual monomer to a very low extent. Thesefavorable results are attributable to the organometallic compound of thepresent invention, because it is highly resistant to heat anddeactivated less in a DCPD polymerization process, which is known to beexothermic and operates at high temperature. Comparing the results ofEXAMPLE 17 and 18 with those of respective COMPARATIVE EXAMPLES 3 and 4,it is demonstrated that the organometallic compound of the presentinvention is more reactive, when incorporated with silicon. Moreover,the effect of a reaction-adjusting agent is observed, when the resultsof EXAMPLE 18 are compared with those of EXAMPLE 20.

Examples 21 to 24

In each of EXAMPLES 21 to 24, DCPD was metathesis-polymerized in thepresence of the organometallic compound of the present invention, asdescribed below, to evaluate moldability of the polymer product.

0.1 mmols ({fraction (1/10,000)} mols of DCPD) of the organometalliccompound of the present invention, represented by the formula (3), (5),(9) or (11), was dissolved in 0.5 g of toluene, and added to 132 g ofDCPD contained in a 100 mL beaker, and the solution was heated at 60° C.The polymerization proceeded while it was stirred by stirrer chips forseveral minutes, and it started to form threads when the liquid surfacewas spooned up by a spatula. However, it no longer formed threads whenits viscosity increased to a certain level; it repelled, like rubber, aspatula put in the solution to spoon up the surface. Gelation time isdefined as a time span from start of the reaction to a point at whichthe solution no longer forms threads. It was used as a relative indexwhich represented time span from start of the polymerization to a pointat which the solution becomes moldable, to evaluate moldability of thepolymer prepared in the presence of each catalyst. The results are givenin Table 4, described later.

Comparative Examples 5 to 7

A polymer was synthesized in each of COMPARATIVE EXAMPLES 5 to 7 usingthe organometallic compound, represented by the formula (20), (21) or(22) and described in Japanese Patent Laid-Open No.11-510807, and itsgelation time was measured in the same manner as in EXAMPLES 21 to 24,to evaluate moldability of the polymer prepared in the presence of eachcatalyst. The results are given in Table 4, described later.

TABLE 4 Evaluation COMPARATIVE COMPARATIVE COMPARATIVE Item EXAMPLE 21EXAMPLE 22 EXAMPLE 23 EXAMPLE 24 EXAMPLE 5 EXAMPLE 6 EXAMPLE 7 Complex 35 9 11 20 21 22 Gelation 6 minutes 6 minutes 5 minutes 7 minutes 10seconds 11 minutes 12 minutes time

An ideal gelation time is around 5 minutes for producing various typesof polymers, when they are to be molded into various shapes while DCPDis polymerized. When the reaction solution is gelled in a shorter time,it may be completely cured before it reaches every part in the mold,making it difficult to produce a desired molded article. When it isgelled in an excessively longer time, on the other hand, the processefficiency may be deteriorated.

As shown in Table 2, the polymer prepared in COMPARATIVE EXAMPLE 5 inthe presence of the organometallic compound represented by the formula(20) is gelled too fast, suggesting that it will be difficult to moldthe polymer into a desired shape. On the other hand, the one prepared ineach of COMPARATIVE EXAMPLES 6 and 7 in the presence of the respectiveorganometallic compound represented by the formula (21) or (22) needs anexcessively long reaction time, suggesting that it may cause significantprocess problems. By contrast, it is demonstrated that the metathesispolymerization reaction in each of EXAMPLES 21 to 24, which proceeds inthe presence of the organometallic compound represented by the formula(3), (5), (9) or (11), is useful for producing desired molded shape foradequate gelation time of the polymer it gives.

Example 25

0.5 mmols of the organometallic compound of the present invention,represented by the formula (3), was put in a 500 mL egg-plant typeflask, to which 1.0 mol of norbornene, 100 mL of toluene and 50 or 100mmols of allyl acetate as a reaction-controlling agent were added, andthe mixture was kept at 40° C. for the ring-opening metathesispolymerization. The product polymer was analyzed for the product yield,number-average molecular weight (Mn) and molecular weight distribution(PDI) to evaluate the effect of the reaction-controlling agent. Theresults are given in Table 5, described later, where these polymerproducts are designated as those prepared in EXAMPLES 25-1 or 25-2.

Comparative Examples 8 to 10

The polymers synthesized in the presence of the organometallic compoundrepresented by the formula (20) or (21) described in Japanese PatentLaid-Open No.11-510807, or of the one represented by the formula (24)described in Chem. Lett., 1999, 369 were evaluated in the same manner asin EXAMPLE 25. The results are given in Table 5, described later, wherethese polymer products are designated as those prepared in COMPARATIVEEXAMPLES 8 to 10-1 or 8 to 10-2.

TABLE 5 Reaction- Number-average Molecular weight controlling agentProduct molecular weight distribution Complex content yield (Mn) (PDI)EXAMPLE 25-1  3 50 mmol >99% 7760 3.76 EXAMPLE 25-2  3 100 mmol  >99%4828 3.04 COMPARATIVE EXAMPLE 8-1 20 50 mmol >99% 69873  18.3COMPARATIVE EXAMPLE 8-2 20 100 mmol  >99% 54839  15.4 COMPARATIVEEXAMPLE 9-1 22 50 mmol 60% 8263 4.01 COMPARATIVE EXAMPLE 9-2 22 100mmol  55% 3987 3.56 COMPARATIVE EXAMPLE 10-1 24 50 mmol 73% 25384  10.8COMPARATIVE EXAMPLE 10-2 24 100 mmol  70% 19987  9.81

As shown in Table 5, the polymerization process of the present inventioncan give a polymer of controlled molecular weight, because it proceedsat an adequate rate in the presence of the organometallic compound ofthe present invention coupled with a reaction-controlling agent. In thesimilar process which uses the organometallic compound in COMPARATIVEEXAMPLE 8, on the other hand, a high-molecular-weight polymer isproduced, because the complex is too active to control the reaction.Moreover, in the similar process which uses the organometallic compoundin COMPARATIVE EXAMPLE 9, the complex is less active than theorganometallic compound represented by the formula (3) of the similarstructure except that it contains silicon, causing reduced product yieldand slightly deteriorated controllability.

It may be difficult for the organometallic compound represented by theformula (24) as a catalyst to control the reaction at a very lowcontent, e.g., {fraction (1/2000)} mols per mol of the monomer as usedin COMPARATIVE EXAMPLE 10, although exhibiting controllability at a veryhigh content, e.g., {fraction (1/20)} mols per mol of the monomer, asdescribed in Chem. Lett., 1999, 369. On the other hand, thepolymerization reaction controlled by the organometallic compound of thepresent invention as a catalyst, which contains silicon, can give awell-controlled polymer in a high yield even at a very low content of{fraction (1/2000)} mols, and hence is advantageous industrially.

Examples 26 to 31

The NMR spectral analysis was conducted in each of EXAMPLES 26 to 31 tomeasure thermal stability of the organometallic compound of the presentinvention in a solution using a Varian Mercury 300 spectrometer underthe conditions of chemical Shifts δ (ppm), 25° C., and standard of1H-NMR: SiMe₄, 31P{1H} NMR: 85% H₃PO₄.

0.025 mmols of the organometallic compound represented by the formula(3), (7), (8), (10), (12) or (13) was put in a nitrogen-purged NMR tube,to which 0.6 mL of distilled toluene was added to dissolve the compoundtherein, and the solution was heated at 80° C. in a nitrogen atmosphere.The 31P{1H} NMR was measured immediately after it reached 80° C. and 6,12 and 24 hours thereafter, to observe its temporal changes, andevaluate stability of each organometallic compound from the spectralintensity. The results are given in Table 6, described later.

Comparative Example 11

The organometallic compound represented by the formula (20) wasevaluated in the same manner as in EXAMPLES 26 to 31. The results aregiven in Table 6, described later.

TABLE 6 Immediately Complex after 6 hours after 12 hours after 24 hoursafter EXAMPLE 26  3 100% 99% 98% 96% EXAMPLE 27  7 100% 98% 95% 90%EXAMPLE 28  8 100% 98% 95% 93% EXAMPLE 29 10 100% 95% 90% 85% EXAMPLE 3012 100% 95% 89% 84% EXAMPLE 31 13 100% 99% 97% 95% COMPARATIVE EXAMPLE11 20 100% 28%  5% —

As shown in Table 6, the organometallic compound prepared in each ofEXAMPLES 26 to 31 almost fully remained undecomposed for 24 hours,suggesting its excellent thermal stability. By contrast, the oneprepared in COMPARATIVE EXAMPLE 11 was almost decomposed in 6 hours, andcompletely in 24 hours. These results indicate that the organometalliccompound of the present invention is excellent in thermal stability.

POSSIBILITY OF INDUSTRIAL UTILIZATION

As described above, the organometallic compound of the present inventionis excellent in resistance to heat and oxygen and also in reactioncontrollability, and high in metathesis activity. As such, the resinproduced in the presence of the organometallic compound as a metathesisreaction catalyst has various advantages over that produced in thepresence of the conventional metathesis reaction catalyst, e.g., higherglass transition temperature and lower residual monomer content toreduce its odor, and can be used for various areas which needcharacteristics of high adhesion, resistance to heat and chemicals, andso on, e.g., electrical/electronic parts, baths and combinedpurification tanks.

The present invention can control molecular weight of the polymer, acharacteristic which the conventional metathesis reaction process isweak in, by the aid of a reaction-controlling agent. Such a polymer isapplicable to adhesive agents and molding aids. Copolymerization of twoor more types of metathesis-reactive monomers can greatly expand theprocess applicable range.

The organometallic compound catalyst of the present invention hasanother advantage, when used for polymerization of a monomer, e.g.,DCPD, to produce a thermosetting resin which needs reaction molding,because it can give a curing speed more suitable for molding processthan does the conventional ruthenium-based catalyst, with the resultthat addition of a third component, e.g., retardant, is not essential.

1. An organometallic compound containing ruthenium or osmium and silicon, represented by the general formula (1):

wherein, M is ruthenium or osmium; R₁ is hydrogen atom, an alkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, carboxyl group of 2 to 20 carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20 carbon atoms, alkylsilyl group of 2 to 20 carbon atoms, arylsilyl group of 2 to 20 carbon atoms or ferrocene derivative, as required, with a phenyl group substituted with an alkyl group of 1 to 5 carbon atoms, halogen atom or alkoxy group of 1 to 5 carbon atoms; R₂ to R₄ are each hydrogen atom, an alkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, carboxyl group of 2 to 20 carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20 carbon atoms, alkylsilyl group of 2 to 20 carbon atoms, arylsilyl group of 2 to 20 carbon atoms or ferrocene derivative, which may be the same or different and substituted, as required, with a phenyl group substituted with an alkyl group of 1 to 5 carbon atoms, halogen atom or alkoxy group of 1 to 5 carbon atoms; when R₁ is hydrogen atom, at least one of R₂ to R₄ is phenyl, isopropyl or t-butyl group; X₁ and X₂ are each an anionic ligand, which may be the same or different; and L₁ and L₂ are each a neutral electron donor, which may be the same or different and at least one of L₁ and L₂ is a phosphorus-based ligand; where 2 or 3 of X₃, X₂, L₁ and L₂ may together form a multidentate, chelated ligand.
 2. The organometallic compound according to claim 1, wherein R₁ in the general formula (1) is a substituent selected from the group consisting of phenyl, anisyl, t-butyl, n-butyl, n-propyl, isopropyl, ethyl, methyl, methoxymethyl, ferrocenyl and trimethylsilyl group.
 3. The organometallic compound according to claim 1, wherein each of R₂ to R₄ in the general formula (1) is a substituent selected from the group consisting of methyl, ethyl, isopropyl, t-butyl, cyclohexyl and phenyl group.
 4. The organometallic compound according to claim 1, wherein each of L₁ and L₂ in the general formula (1) is a phosphorus-based ligand.
 5. An organometallic compound containing ruthenium or osmium and silicon, represented by the general formula (2):

wherein, M is ruthenium or osmium; R₅ is hydrogen atom, an alkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, substituted phenyl group of 7 to 20 carbon atoms, carboxyl group of 2 to 20 carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20 carbon atoms, alkylsilyl group of 2 to 20 carbon atoms or arylsilyl group of 2 to 20 carbon atoms; R₆ to R₈ are each hydrogen atom, an alkenyl group of 2 to 20 carbon atoms, alkyl group of 1 to 20 carbon atoms, aryl group of 6 to 20 carbon atoms, carboxyl group of 2 to 20 carbon atoms, alkoxy group of 2 to 20 carbon atoms, alkenyloxy group of 2 to 20 carbon atoms, aryloxy group of 6 to 20 carbon atoms, alkoxycarbonyl group of 2 to 20 carbon atoms, alkylthio group of 2 to 20 carbon atoms, alkylsilyl group of 2 to 20 carbon atoms, arylsilyl group of 2 to 20 carbon atoms or ferrocene derivative, which may be the same or different and substituted, as required, with a phenyl group substituted with an alkyl group of 1 to 5 carbon atoms, halogen atom or alkoxy group of 1 to 5 carbon atoms; when R₅ is hydrogen atom, at least one of R₆ to R₈ is phenyl, isopropyl or t-butyl group; X₃ and X₄ are each a halogen atom, which may be the same or different; and L₃ and L₄ are each a neutral electron donor, which may be the same or different; where 2 or 3 of X₃, X₄, L₃ and L₄ may together form a multidentate, chelated ligand.
 6. The organometallic compound according to claim 5, wherein R₅ in the general formula (2) is a substituent selected from the group consisting of tolyl, anisyl, t-butyl, n-butyl, n-propyl, isopropyl, ethyl, methyl, methoxymethyl and trimethylsilyl group.
 7. The organometallic compound according to claim 5, wherein each of R₆ to R₈ in the general formula (2) is a substituent selected from the group consisting of methyl, ethyl, isopropyl, t-butyl, cyclohexyl and phenyl group.
 8. The organometallic compound according to claim 5, wherein each of L₃ and L₄ in the general formula (2) is a phosphorus-based ligand.
 9. A process for producing the organometallic compound according to claim 1, wherein a precursor for a ruthenium or osmium complex and neutral electron-donating ligand compound are mixed with each other for the ligand-exchanging reaction.
 10. A metathesis reaction catalyst containing the organometallic compound according to claim
 1. 11. A metathesis polymerization process for producing a metathesis-reactive monomer in the presence of the metathesis reaction catalyst according to claim
 10. 12. The metathesis polymerization process according to claim 11, wherein said metathesis-reactive monomer is a norbornene-based monomer of bicyclic or higher structure.
 13. The metathesis polymerization process according to claim 11, wherein said norbornene-based monomer is a compound selected from the group consisting of norbornene, substituted norbornene, dicyclopentadiene and tricyclopentadiene.
 14. The metathesis polymerization process according to one of claims 11 to 13, wherein 2 or more metathesis-reactive monomers are copolymerized.
 15. The metathesis polymerization process according to one of claims 11 to 13, wherein a reaction-adjusting agent is further incorporated.
 16. The metathesis polymerization process according to claim 15, wherein said reaction-adjusting agent is an acidic component.
 17. The metathesis polymerization process according to claim 16, wherein said acidic component is a Bronsted acid (protonic acid).
 18. The metathesis polymerization process according to one of claims 11 to 13, wherein a reaction-controlling agent is further incorporated.
 19. The metathesis polymerization process according to claim 18, wherein said reaction-controlling agent is a compound having a metathesis-reactive unsaturated bond.
 20. The metathesis polymerization process according to claim 19, wherein said compound having a metathesis-reactive unsaturated bond is selected from the group consisting of a vinyl ester, vinyl sulfide, vinyl ether, vinyl pyrrolidone, allyl ester and allyl sulfide. 